Isotope Ratio Mass Spectrometry

SmartNotes
How do isotope fingerprints support forensic
investigations?
Introduction
Forensic investigations examine sample materials to determine how similar or
different they are, or to identify the origin of the material. Identifying the difference
in a material or where it comes from can be achieved because materials have a
unique chemical signature, like a fingerprint. To visualize this fingerprint, Isotope
Ratio Mass Spectrometry (IRMS) is used, measuring the stable isotopes of
sample material that are essentially chemically identical. Unlike other types of
inferential evidence in forensic investigations (e.g., bite marks, impression marks
from tires or footwear, handwriting), isotope measurements are quantitative
empirical evidence that are reproducible and easy to validate. The application of
isotope fingerprints to forensic investigations has become more commonplace
because there is a need for a rigorous scientific foundation underpinned by
sound analytical techniques. Application areas include forensic investigations on
human, criminal, environmental, ecological, food and archaeological materials.
Isotope fingerprints in forensics
Isotope fingerprints in forensic materials are related to
natural processes and geographical regions and can
define differences in sample materials. This means that
forensic sample materials can be put into a geographical
context, so that their origin can be traced, or understood
with respect to a specific process or set of processes in
nature, such as botanical (timber, food, skeletal remains),
dietary and food web variations (skeletal and animal
remains, human and animal tissue) and geographical
Table 1.
location (skeletal remains, narcotics, explosives,
packaging, gemstones). Table 1 provides a non-
exhaustive summary of isotope fingerprints in forensic
applications. These natural process can be traced using
carbon, nitrogen, sulfur, oxygen and hydrogen isotope
fingerprints encoded in the sample materials. However,
in the case of explosives, these isotope fingerprints trace
factory production efficiency and processes.

Isotope What sample types

What is the biogeochemical interpretation? Example forensic interpretation
Fingerprint can be analyzed?
Botanical processes (C3, C4 and CAM
Human (dietary preferences, travel Bones, teeth, hair, nails,
Photosynthesis), plant rate of uptake of carbon
history, and provenance), food food, timber origin, oil,
Carbon (differentiate region plant is from, such as tropical vs.
(labelling authenticity) tracing narcotics, cellotape,
temperate), source rock geology, factory production
packaging, arson matchsticks
processes/batch processes

Nitrogen fixation (trophic level differentiation: Human (dietary preferences, travel Bones, teeth, hair, nails,
Nitrogen herbivore vs. carnivore vs. omnivore), history, and provenance), food food, explosives, oil,
factory production processes (labelling, authenticity) narcotics

Incorporated into plant and animal tissue from

Bones, teeth, hair, nails,
bedrock uptake/weathering, atmospheric deposition Human (dietary preferences and
Sulfur food, timber origin, human
(sea spray, geological origins, pollution) and provenance), food (origin)
and animal tissue, oil
microbial activity

Human (travel history and

Bones, teeth, hair, nails,
Principally related to local-regional rainfall, or water provenance), synthetic and narcotics
animal horn, narcotics, food
Hydrogen transport regimes, and hence geographical area, (geographical origin), food and
and beverage, timber origin,
factory production processes/batch processes beverage (authenticity and origin),
oil, matchsticks
tracing packaging, arson

Human (travel history and

Bones, teeth, hair, nails,
Mainly related to local-regional rainfall, or water provenance), synthetic and narcotics
animal horn, narcotics, food
Oxygen transport regimes, and hence geographical area, (geographical origin), food and
and beverage, timber origin,
factory production efficiency beverage (authenticity and origin),
explosives, matchsticks
tracing packaging, arson
The application of isotope fingerprints in forensics brings
unique capabilities to the laboratory and to the forensics
field that increasingly demands a quantitative empirical
evidence base that is reproducible and easy to validate.
Applying isotope fingerprints to forensic questions allows
investigators to provide a unique characterization of
the sample material and so trace reactants, chemical
pathways and reaction conditions, relative to natural
processes, and then compare materials of interest to
others collected, or to an authentic reference material1.
In addition, investigators may also implement predictive
models for environmental parameters, such as rainfall,
geological bedrock, temperature, land use, for example1.
From this basis, using isotope fingerprints makes it
possible to determine similarities between different drug
seizures and authentic material and to follow trafficking
routes to their original source2. The same principle can
be applied to other criminal materials such as explosives1,
artefacts and gemstones, human remains, human and
animal migration and movements, oil spills, food and
beverage origin and authenticity, synthetic drugs, arson
investigations and plant and wood product origin, and
be used to answer questions on material origin and
authenticity1.
Analytical solution for detecting isotope
fingerprints
IRMS works by measuring the “isotope fingerprint”
of a sample, a unique chemical signature that changes
from sample to sample. There are a number of
approaches to preparing sample materials for isotope
analysis. However, the fundamental process for IRMS
is the conversion of a solid or liquid sample to a gas
under high temperature. In the case of EA-IRMS and
GC-IRMS the conversion of the sample to a gas is
performed by two processes: combustion and pyrolysis.
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Combustion, burning the sample at around 1000 ˚C
with oxygen, is used to evolve carbon, nitrogen and
sulfur from the sample in the form of N2, CO2 and SO2.
Pyrolysis, breaking down the sample at 1400 ˚C in a
reductive environment, is used to evolve hydrogen and
oxygen from the sample, in the form of H2 and CO. After
the gases are produced, they are separated from one
another using gas chromatography and then transferred
in a continuous gas flow to a detector that measures
the isotope fingerprint of the sample. In addition, gas
samples can be directly analyzed.
The dedicated solutions of the Thermo Fisher Scientific™
stable isotope portfolio are designed to offer different
capabilities and performances, with dedicated features
for the coupling to the Thermo Scientific™ IRMS Systems,
according to the varying analytical needs of laboratories
working for routine and research applications:
• the Thermo Scientific™ EA IsoLink™ IRMS System, for
analysis of bulk sample material;
• the Thermo Scientific™ GC IsoLink II™ IRMS System,
for analyzing specific compounds from a bulk sample
material;
• the Thermo Scientific™ LC IsoLink™ IRMS System, for
analyzing specific compounds from a bulk sample
material in liquid form;
• the Thermo Scientific™ GasBench II System, for the
analysis of gas samples evolved from bulk sample
materials.
References
1. Chesson, L.A., Tipple, B.J., Howa, J.D., Bowen, G.J., Barnette, J.E., Cerling, T.E.,
Ehleringer, J.R. Treatise on geochemistry (2nd Ed.), Vol. 14, 285-317.
2. Mallette, J. R., Casale, J.F., Jordan, J., Morello, D.R., Beyer, P.M. Nature Sci. Rep.
23520-23530.